WO2012088683A1 - Porous graphene material and preparation method and uses as electrode material thereof - Google Patents

Porous graphene material and preparation method and uses as electrode material thereof Download PDF

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WO2012088683A1
WO2012088683A1 PCT/CN2010/080464 CN2010080464W WO2012088683A1 WO 2012088683 A1 WO2012088683 A1 WO 2012088683A1 CN 2010080464 W CN2010080464 W CN 2010080464W WO 2012088683 A1 WO2012088683 A1 WO 2012088683A1
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porous graphene
porous
graphene material
graphene
pore
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PCT/CN2010/080464
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French (fr)
Chinese (zh)
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周明杰
王要兵
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海洋王照明科技股份有限公司
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Priority to CN201080069747.2A priority Critical patent/CN103180243B/en
Priority to EP10861242.5A priority patent/EP2660198A4/en
Priority to PCT/CN2010/080464 priority patent/WO2012088683A1/en
Priority to US13/883,414 priority patent/US20130230709A1/en
Priority to JP2013546552A priority patent/JP2014507365A/en
Publication of WO2012088683A1 publication Critical patent/WO2012088683A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to an electrode material, and more particularly to a porous graphene material, a method for preparing the same, and an application as an electrode material.
  • Single-layer graphene has a large specific surface area, excellent electrical conductivity, thermal conductivity, and low coefficient of thermal expansion.
  • its high conductivity properties, large specific surface properties and its two-dimensional nanoscale structural properties of monolayers can be used as electrode materials in supercapacitors and lithium ion batteries.
  • the porous graphene material is composed of a multi-layer graphene monolayer structure, has high mechanical strength, is not easy to agglomerate, and thus has broad application prospects.
  • a porous graphene material having a pore diameter of 1 nm to 10 ⁇ m and a specific surface area of 100 m 2 /g to 2000 m 2 /g.
  • the porous graphene material has a pore diameter of 50 nm to 10 ⁇ m, and the total volume is 20% to 40%, and 2 nm to 50 nm. It accounts for 35% ⁇ 55% of the total volume, and 1nm ⁇ 2nm accounts for 20% ⁇ 25% of the total volume.
  • the pore size of the porous material is graphene 2 ⁇ 50nm, specific surface area of 150m 2 / g ⁇ 1000m 2 / g.
  • the porous graphene material has a pore specific surface area of from 150 m 2 /g to 2500 m 2 /g.
  • a method for preparing a porous graphene material comprising the steps of:
  • the porous graphene material is obtained by heating the composite to release a gas from the pore former.
  • the pore forming agent is dry ice, and the heating temperature vaporizes the dry ice.
  • the pore former has a decomposition temperature lower than 2000 ° C
  • the organic polymer material or the organic small molecule material such that the pore former in the composite releases a gas by heating the composite to 500 ⁇ 2000 °C, the organic polymer material or organic small molecular material is thermally decomposed to release gas.
  • the organic polymer material is polycarbonate pellet, polystyrene pellet, polypropylene pellet, polyacetylene pellet, polyphenylene pellet, polydimethylsiloxane pellet, polycarbonate One or more of ester nanoparticles, polystyrene nanoparticles, polypropylene nanoparticles, polyacetylene nanoparticles, polyphenyl nanoparticles, and polydimethylsiloxane nanoparticles;
  • the organic small molecule material is one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate, and potassium permanganate.
  • the organic polymer material has a small sphere diameter of 10 nm to 1 ⁇ m.
  • the porous graphene material can be used as a supercapacitor or lithium ion battery electrode material.
  • the preparation method of the porous graphene material is obtained by mixing graphene or graphene with a pore former and pressing to obtain a composite, and then releasing the pore former in the composite to release a gas, if it is graphene oxide, 500 ⁇ 2000 The heat treatment is carried out at °C, and finally the porous graphene material is obtained.
  • the preparation method has simple process, and the prepared porous graphene material has a large specific surface area, which is favorable for macroscopic processing, and the obtained porous graphene material can be used as a supercapacitor and a lithium ion battery. Electrode material.
  • FIG. 1 is a flow chart showing a method of preparing a porous graphene material according to an embodiment
  • Example 2 is a SEM picture of the doped composite prepared in Example 4.
  • a porous graphene material having a pore diameter of 1 nm to 10 ⁇ m and a specific surface area of 100 m 2 /g to 2000 m 2 /g.
  • the above porous graphene material has a pore diameter of 50 nm to 10 ⁇ m and accounts for 20% to 40% of the total volume, and the pore diameter is 2nm ⁇ 50nm accounts for 35% ⁇ 55% of the total volume, and the pore size is 1nm ⁇ 2nm, which accounts for 20% ⁇ 25% of the total volume.
  • the diameter of the porous material is graphene 2 ⁇ 50nm, specific surface area of 150m 2 / g ⁇ 1000m 2 / g.
  • the porous graphene material has a pore specific surface area of from 150 m 2 /g to 2500 m 2 /g.
  • This porous graphene material has a high specific surface area and a specific surface area, and can be used as an electrode material for supercapacitors and lithium ion batteries.
  • the method for preparing a porous graphene material as shown in FIG. 1 uses graphene to prepare a porous graphene material, comprising the following steps:
  • the graphene or graphene oxide is mixed with a pore former capable of releasing a gas, and a composite of bulk or powdery particles is pressed.
  • the pore former selects a substance that can release gas. Generally, it can be dry ice, and the decomposition temperature is lower than 2000 °C. Organic polymer materials and organic small molecule materials, different pore-forming agents are selected, and the specific reaction conditions are different.
  • the pore former is selected to be mixed with graphene in the form of a powdered material or solution.
  • dry ice When using dry ice as a pore former, select dry ice powder and graphene or graphene oxide powder with dry ice powder at -40 °C Under mixing, pressing into a bulk material or nano-scale particles, that is, obtaining a composite.
  • an organic polymer material or an organic small molecule material is used as a pore-forming agent
  • an organic polymer material powder or an organic small molecule material powder or a solution is selected, and the graphene or graphene oxide powder is mixed with a pore former in a solvent, or The powdery pore former is mixed, the solvent is removed or the temperature is lowered, solidified, pressed into a bulk material or nanometer-sized particles to obtain a composite.
  • the organic polymer selects an organic polymer which can be carbonized into carbon or gas at a high temperature, including: polycarbonate beads, polystyrene beads, polypropylene beads, polyacetylene beads, polyphenylene beads, polydimethylsiloxane One or more of oxyalkylene beads, polycarbonate nanoparticles, polystyrene nanoparticles, polypropylene nanoparticles, polyacetylene nanoparticles, polyphenyl nanoparticles, and polydimethylsiloxane nanoparticles.
  • the organic small molecule selects small organic molecules which can be pyrolyzed into a gas, including: one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate and potassium permanganate.
  • a gas including: one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate and potassium permanganate.
  • the composite obtained in S10 is heated to 500 ⁇ 2000 °C, thermal decomposition of organic polymer materials or organic small molecular materials, partial removal of decomposition products in vacuum, solvent washing after passivation, drying to obtain porous graphene materials.
  • the surface of graphene oxide is mainly composed of -C-OH or carbon-carbon epoxy bond. Under high temperature conditions, two -OH will lose one water molecule, and at the same time form a carbon-oxygen double bond, and the carbon-oxygen double bond will be formed. Carbon monoxide gas, carbon-carbon epoxy bond also forms a carbon-oxygen double bond at a high temperature to form a carbon monoxide gas. This causes O in the graphene oxide to be removed, thereby obtaining graphene.
  • a mixed atmosphere of H 2 and Ar can be selected.
  • the graphene and graphene oxide in step S10 can be obtained by the following steps:
  • graphite oxide can be prepared by the Hummers method, that is, S10
  • the obtained graphite, potassium permanganate and high-concentration strong oxidizing acid (sulfuric acid or nitric acid) are heated in a water bath or an oil bath in the same container, and are taken out after being fully oxidized, firstly reducing potassium permanganate with hydrogen peroxide, using distilled water or The product was washed several times with hydrochloric acid and dried to obtain graphite oxide.
  • the process is carried out to improve the preparation of graphene oxide to improve the yield and product purity.
  • the improved preparation process comprises the following steps.
  • the pretreated mixture and potassium permanganate are added to concentrated sulfuric acid to keep the temperature below 20 °C. 30 ⁇ 40 °C oil bath 1.5 ⁇ 2 h, add deionized water, add hydrogen peroxide reaction after 15 min, suction filtration and collect solid.
  • the purpose of the oil bath is to better control the reaction temperature, and in other embodiments, a water bath can also be used.
  • graphene oxide is mixed with deionized water and dispersed into a suspension.
  • Ultrasonic ultrasonic dispersion of graphene oxide can generally be employed.
  • the reducing agent is a soluble compound having a certain thermal stability, and generally, hydrazine hydrate, sodium borohydride and terephthalic acid, preferably hydrazine hydrate are mentioned.
  • the preparation method of the porous graphene material is obtained by mixing graphene or graphene with a pore former and pressing to obtain a composite, and then releasing the pore former in the composite to release a gas, if it is graphene oxide, 500 ⁇ 2000 The heat treatment is carried out at °C, and finally the porous graphene material is obtained.
  • the preparation method has simple process, and the prepared porous graphene material has a large specific surface area, which is favorable for macroscopic processing, and the obtained porous graphene material can be used as a supercapacitor and a lithium ion battery. Electrode material.
  • the specific step is to add 20g of 50 mesh graphite powder, 10g of potassium persulfate and 10g of phosphorus pentoxide to 80 °C.
  • concentrated sulfuric acid stir evenly, cool for more than 6h, wash to neutral, and dry.
  • the dried sample was added to 0 ° C, 230 mL of concentrated sulfuric acid, and then 60 g of potassium permanganate was added, and the temperature of the mixture was maintained at After 20 ° C, then in an oil bath at 35 ° C for 2 h, slowly add 920 mL of deionized water.
  • the porous graphene material obtained in Example 1 had a specific surface area a s of 136.14 m 2 /g, an average pore diameter d p of 8.0156 nm, and a pore specific surface area a p of 264.88 m 2 /g.
  • the porous graphene material obtained in Example 2 had a specific surface area a s of 193.12 m 2 /g, an average pore diameter d p of 6.4984 nm, and a pore specific surface area a p of 273.94 m 2 /g.
  • the porous graphene material obtained in Example 3 had a specific surface area a s of 422.41 m 2 /g, an average pore diameter d p of 9.2264 nm, and a pore specific surface area a p of 655.9 m 2 /g.
  • Figure 3 shows the SEM of the porous graphene material prepared by graphene and polystyrene beads. As the photograph, it can be seen that the porous graphene material has a porous structure.
  • the porous graphene material obtained in Example 4 had a specific surface area a s of 134.66 m 2 /g, an average pore diameter d p of 7.9471 nm, and a pore specific surface area a p of 242.69 m 2 /g.
  • the heat treatment causes the polypropylene to be thermally decomposed, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.
  • the porous graphene material obtained in Example 5 had a specific surface area a s of 632.41 m 2 /g, an average pore diameter d p of 10.232 nm, and a pore specific surface area a p of 712.52 m 2 /g.
  • the porous graphene material obtained in Example 6 had a specific surface area a s of 901.25 m 2 /g, an average pore diameter d p of 12.547 nm, and a pore specific surface area a p of 845.12 m 2 /g.
  • the graphene is mixed with the ammonium carbonate solution to remove the solvent, solidified, and pressed into a bulk material.
  • the heat treatment causes the polydimethylsiloxane to thermally decompose, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.

Abstract

A porous graphene material and preparation method thereof are provided. The pore diameter of the porous graphene material is 1 nm-10 µm and its specific surface area is 100m2/g-2000m2/g. The method for preparing the porous graphene material comprises the following steps: mixing graphene or graphene oxide with pore-forming agent, and pressing to obtain bulk or powder particle composite; heating the composite, and releasing gases from the pore-forming agent to obtain the porous graphene material. The porous graphene material can be used as electrode materials of supercapacitor and lithium ion battery.

Description

多孔石墨烯材料及其制备方法和作为电极材料的应用Porous graphene material, preparation method thereof and application as electrode material
【技术领域】[Technical Field]
本发明涉及一种电极材料，尤其涉及一种多孔石墨烯材料及其制备方法和作为电极材料的应用。 The present invention relates to an electrode material, and more particularly to a porous graphene material, a method for preparing the same, and an application as an electrode material.
【背景技术】  【Background technique】
自从英国曼彻斯特大学的安德烈 · K · 海姆( Andre K. Geim ) 等在 2004 年制备出石墨烯材料，由于其独特的结构和光电性质受到了人们广泛的重视。它所具有的许多新颖而独特的性质与潜在的应用正吸引了诸多科技工作者。单层石墨烯具有大的比表面积，优良的导电、导热性能和低的热膨胀系数。如：1. 高强度，杨氏摩尔量，( 1,100 GPa ) ，断裂强度：( 125GPa ) ；2. 高热导率，( 5,000 W/mK ) ；3. 高导电性、载流子传输率，( 200,000 cm 2 /V*s ) ；4. 高的比表面积，(理论计算值： 2,630 m2 /g ) 。尤其是其高导电性质，大的比表面性质和其单分子层二维的纳米尺度的结构性质，可在超级电容器和锂离子电池中用作电极材料。 Since the preparation of graphene materials in 2004 by Andre K. Geim of the University of Manchester in the United Kingdom, it has received extensive attention due to its unique structure and optoelectronic properties. Many of its novel and unique properties and potential applications are attracting many scientists. Single-layer graphene has a large specific surface area, excellent electrical conductivity, thermal conductivity, and low coefficient of thermal expansion. Such as: 1. High strength, Young's molar amount, (1,100 GPa), breaking strength: (125GPa); 2. High thermal conductivity, (5,000 W/mK); 3. High conductivity, carrier transport rate, ( 200,000 cm 2 /V*s ) ; 4. High specific surface area, (theoretical calculated value: 2,630 m 2 /g). In particular, its high conductivity properties, large specific surface properties and its two-dimensional nanoscale structural properties of monolayers can be used as electrode materials in supercapacitors and lithium ion batteries.
然而,实际过程中，由于石墨烯单层结构之间，由于强的 π - π 相互作用力，导致它们之间容易发生团聚，导致比表面积的极大的降低，从而使得其在材料方面的应用受到了极大的限制。 However, in the actual process, due to the strong π - π between the graphene monolayer structures The interaction forces cause agglomeration between them, resulting in a great reduction in specific surface area, which makes its application in materials extremely limited.
多孔石墨烯材料由多层石墨烯单层结构组成，具有较高的机械强度，不易发生团聚，因而有着广泛的应用前景。 The porous graphene material is composed of a multi-layer graphene monolayer structure, has high mechanical strength, is not easy to agglomerate, and thus has broad application prospects.
然而，如何方便的得到多孔石墨烯材料是目前电极材料领域的一个难题。 However, how to conveniently obtain porous graphene materials is a difficult problem in the field of electrode materials.
【发明内容】  [Summary of the Invention]
基于此，有必要提供了一种工艺简便的多孔石墨烯材料的制备方法和采用上述制备方法制得的多孔石墨烯材料，以及多孔石墨烯材料在超级电容器或锂离子电池电极材料方面的应用。 Based on this, it is necessary to provide a process for preparing a porous graphene material with simple process and a porous graphene material obtained by the above preparation method, and a porous graphene material for use in a supercapacitor or a lithium ion battery electrode material.
一种多孔石墨烯材料，所述多孔石墨烯材料的孔径为 1nm ~10 μ m ，比表面积为 100m2 /g~2000m2/g 。A porous graphene material having a pore diameter of 1 nm to 10 μm and a specific surface area of 100 m 2 /g to 2000 m 2 /g.
优选的，所述多孔石墨烯材料孔径 50nm ~10 μ m 占总体积 20%~40% ， 2nm~50nm 占总体积 35%~55% ， 1nm~2nm 占总体积 20%~25% 。 Preferably, the porous graphene material has a pore diameter of 50 nm to 10 μm, and the total volume is 20% to 40%, and 2 nm to 50 nm. It accounts for 35%~55% of the total volume, and 1nm~2nm accounts for 20%~25% of the total volume.
优选的，所述多孔石墨烯材料的孔径为 2~50nm ，比表面积为 150m2 /g~1000m2/g 。Preferably, the pore size of the porous material is graphene 2 ~ 50nm, specific surface area of 150m 2 / g ~ 1000m 2 / g.
优选的，所述多孔石墨烯材料的孔比表面积为150 m2/g~2500m2/g。Preferably, the porous graphene material has a pore specific surface area of from 150 m 2 /g to 2500 m 2 /g.
一种多孔石墨烯材料的制备方法，包括如下步骤： A method for preparing a porous graphene material, comprising the steps of:
将石墨烯或氧化石墨烯与可以释放出气体的造孔剂混合、压制块状或粉末状颗粒的复合物； Mixing graphene or graphene oxide with a pore former capable of releasing a gas, and pressing a composite of bulk or powdery particles;
加热所述复合物，使造孔剂释放出气体后，得到所述多孔石墨烯材料。 The porous graphene material is obtained by heating the composite to release a gas from the pore former.
优选的，所述造孔剂为干冰，加热温度使干冰气化。 Preferably, the pore forming agent is dry ice, and the heating temperature vaporizes the dry ice.
优选的，所述造孔剂为分解温度低于 2000 ℃ 的有机高分子材料或有机小分子材料，使所述复合物中的造孔剂释放出气体的操作为：将所述复合物升温至 500~2000℃，使得有机高分子材料或有机小分子材料热分解释放出气体。 Preferably, the pore former has a decomposition temperature lower than 2000 ° C The organic polymer material or the organic small molecule material, such that the pore former in the composite releases a gas by heating the composite to 500~2000 °C, the organic polymer material or organic small molecular material is thermally decomposed to release gas.
优选的，所述的有机高分子材料为聚碳酸酯小球、聚苯乙烯小球、聚丙烯小球、聚乙炔小球、聚苯小球、聚二甲基硅氧烷小球、聚碳酸酯纳米微粒、聚苯乙烯纳米微粒、聚丙烯纳米微粒、聚乙炔纳米微粒、聚苯纳米微粒和聚二甲基硅氧烷纳米微粒中的一种或几种； Preferably, the organic polymer material is polycarbonate pellet, polystyrene pellet, polypropylene pellet, polyacetylene pellet, polyphenylene pellet, polydimethylsiloxane pellet, polycarbonate One or more of ester nanoparticles, polystyrene nanoparticles, polypropylene nanoparticles, polyacetylene nanoparticles, polyphenyl nanoparticles, and polydimethylsiloxane nanoparticles;
有机小分子材料为醋酸铵、碳酸铵、醋酸四甲基铵、硝酸铵、碳酸氢钠、碱式碳酸铜和高锰酸钾中的一种或几种。 The organic small molecule material is one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate, and potassium permanganate.
优选的，所述有机高分子材料的小球直径为 10nm~1 μ m 。 Preferably, the organic polymer material has a small sphere diameter of 10 nm to 1 μm.
优选的，所述多孔石墨烯材料可以用作超级电容器或锂离子电池电极材料。 Preferably, the porous graphene material can be used as a supercapacitor or lithium ion battery electrode material.
这种多孔石墨烯材料的制备方法通过氧化石墨烯或石墨烯与造孔剂混合、压制得到复合物，然后使复合物中的造孔剂释放出气体后，若为氧化石墨烯则500~2000℃热处理，最后得到多孔石墨烯材料，这种制备方法工艺简便，制备出的多孔石墨烯材料比表面积大，有利于宏观加工处理，所得到的多孔石墨烯材料可以用作超级电容器和锂离子电池电极材料。 The preparation method of the porous graphene material is obtained by mixing graphene or graphene with a pore former and pressing to obtain a composite, and then releasing the pore former in the composite to release a gas, if it is graphene oxide, 500~2000 The heat treatment is carried out at °C, and finally the porous graphene material is obtained. The preparation method has simple process, and the prepared porous graphene material has a large specific surface area, which is favorable for macroscopic processing, and the obtained porous graphene material can be used as a supercapacitor and a lithium ion battery. Electrode material.
【附图说明】 [Description of the Drawings]
图 1 为一实施方式的多孔石墨烯材料的制备方法的流程图； 1 is a flow chart showing a method of preparing a porous graphene material according to an embodiment;
图 2 为实施例4制备的掺杂的复合物的SEM图片。 2 is a SEM picture of the doped composite prepared in Example 4.
【具体实施方式】  【detailed description】
下面结合附图及实施例对多孔石墨烯材料及其制备方法做进一步的解释说明。 The porous graphene material and its preparation method will be further explained below with reference to the accompanying drawings and examples.
一种多孔石墨烯材料，孔径为 1nm ~10 μ m ，比表面积为 100m2 /g~2000m2/g 。A porous graphene material having a pore diameter of 1 nm to 10 μm and a specific surface area of 100 m 2 /g to 2000 m 2 /g.
上述多孔石墨烯材料孔径为 50nm ~10 μ m 的占总体积的 20%~40% ，孔径为 2nm~50nm 的占总体积的 35%~55% ，孔径为 1nm~2nm 的占总体积 20%~25% 。 The above porous graphene material has a pore diameter of 50 nm to 10 μm and accounts for 20% to 40% of the total volume, and the pore diameter is 2nm~50nm accounts for 35%~55% of the total volume, and the pore size is 1nm~2nm, which accounts for 20%~25% of the total volume.
在优选的实施例中，多孔石墨烯材料的孔径为 2~50nm ，比表面积为 150m2 /g~1000m2/g 。In a preferred embodiment, the diameter of the porous material is graphene 2 ~ 50nm, specific surface area of 150m 2 / g ~ 1000m 2 / g.
在优选的实施例中，多孔石墨烯材料的孔比表面积为 150 m2 /g~2500m2/g 。In a preferred embodiment, the porous graphene material has a pore specific surface area of from 150 m 2 /g to 2500 m 2 /g.
这种多孔石墨烯材料具有较高的比表面积和孔比表面积，可以用作超级电容器和锂离子电池电极材料。 This porous graphene material has a high specific surface area and a specific surface area, and can be used as an electrode material for supercapacitors and lithium ion batteries.
如图 1 所示的多孔石墨烯材料的制备方法，采用石墨烯制备多孔石墨烯材料，包括如下步骤： The method for preparing a porous graphene material as shown in FIG. 1 uses graphene to prepare a porous graphene material, comprising the following steps:
S10 、石墨烯或氧化石墨烯与造孔剂混合、压制得到复合物 S10, graphene or graphene oxide mixed with a pore former and pressed to obtain a composite
将石墨烯或氧化石墨烯与可以释放出气体的造孔剂混合、压制块状或粉末状颗粒的复合物。 The graphene or graphene oxide is mixed with a pore former capable of releasing a gas, and a composite of bulk or powdery particles is pressed.
造孔剂选择可以释放出气体的物质，一般可以为干冰、分解温度低于 2000 ℃ 有机高分子材料和有机小分子材料，选择不同的造孔剂，具体反应条件不同。 The pore former selects a substance that can release gas. Generally, it can be dry ice, and the decomposition temperature is lower than 2000 °C. Organic polymer materials and organic small molecule materials, different pore-forming agents are selected, and the specific reaction conditions are different.
一般的，造孔剂选择以粉末状材料或溶液的形式与石墨烯混合。 Typically, the pore former is selected to be mixed with graphene in the form of a powdered material or solution.
以干冰作为造孔剂时，选择干冰粉末，将石墨烯或氧化石墨烯粉末与干冰粉末在 -40 ℃ 下混合，压制成块状材料或是纳米级别的微粒，即得到复合物。 When using dry ice as a pore former, select dry ice powder and graphene or graphene oxide powder with dry ice powder at -40 °C Under mixing, pressing into a bulk material or nano-scale particles, that is, obtaining a composite.
以有机高分子材料或有机小分子材料作为造孔剂时，选择有机高分子材料粉末或有机小分子材料粉末或溶液，将石墨烯或氧化石墨烯粉末与造孔剂在溶剂中混合，或与粉末状造孔剂混合，除去溶剂或降低温度，固化、压制成块状材料或是纳米级别的微粒，即得到复合物。 When an organic polymer material or an organic small molecule material is used as a pore-forming agent, an organic polymer material powder or an organic small molecule material powder or a solution is selected, and the graphene or graphene oxide powder is mixed with a pore former in a solvent, or The powdery pore former is mixed, the solvent is removed or the temperature is lowered, solidified, pressed into a bulk material or nanometer-sized particles to obtain a composite.
有机高分子选择可以高温碳化成碳或气体的有机高分子，包括：聚碳酸酯小球、聚苯乙烯小球、聚丙烯小球、聚乙炔小球、聚苯小球、聚二甲基硅氧烷小球、聚碳酸酯纳米微粒、聚苯乙烯纳米微粒、聚丙烯纳米微粒、聚乙炔纳米微粒、聚苯纳米微粒和聚二甲基硅氧烷纳米微粒中的一种或几种。 The organic polymer selects an organic polymer which can be carbonized into carbon or gas at a high temperature, including: polycarbonate beads, polystyrene beads, polypropylene beads, polyacetylene beads, polyphenylene beads, polydimethylsiloxane One or more of oxyalkylene beads, polycarbonate nanoparticles, polystyrene nanoparticles, polypropylene nanoparticles, polyacetylene nanoparticles, polyphenyl nanoparticles, and polydimethylsiloxane nanoparticles.
有机小分子选择可以高温分解为气体的有机小分子，包括：醋酸铵、碳酸铵、醋酸四甲基铵、硝酸铵、碳酸氢钠、碱式碳酸铜和高锰酸钾中的一种或几种。 The organic small molecule selects small organic molecules which can be pyrolyzed into a gas, including: one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate and potassium permanganate. Kind.
S20 、复合物加热，使造孔剂释放出气体后，得到多孔石墨烯材料 S20, the composite is heated, and the pore former releases gas, and the porous graphene material is obtained.
根据不同的造孔剂，具体反应条件略有不同。 The specific reaction conditions vary slightly depending on the pore former.
选择干冰作为造孔剂时，将 S10 得到的复合物逐步升温到室温，真空干燥除去干冰，若为石墨烯复合物，钝化即可得到多孔石墨烯材料；若为氧化石墨烯复合物，需要再对氧化石墨烯复合物在 500~2000℃进行热处理，热还原得到多孔石墨烯材料。 When using dry ice as a pore former, S10 The obtained composite is gradually heated to room temperature, and dried under vacuum to remove dry ice. If it is a graphene composite, passivation can obtain a porous graphene material; if it is a graphene oxide composite, it is necessary to further form a graphene oxide composite. The heat treatment is carried out at 500 to 2000 ° C, and the porous graphene material is obtained by thermal reduction.
选择有机高分子材料或有机小分子材料作为造孔剂时，将 S10 得到的复合物加热到 500~2000℃，热分解除去有机高分子材料或有机小分子材料，真空除去部分分解产物，钝化后溶剂洗涤，干燥后得到多孔石墨烯材料。 When an organic polymer material or an organic small molecule material is selected as a pore former, the composite obtained in S10 is heated to 500~2000 °C, thermal decomposition of organic polymer materials or organic small molecular materials, partial removal of decomposition products in vacuum, solvent washing after passivation, drying to obtain porous graphene materials.
氧化石墨烯的表面主要是以-C-OH或者碳碳环氧键存在，高温条件下，两个-OH会失去一个水分子，同时形成一个碳氧双键，碳氧双键会脱去形成一氧化碳气体，碳碳环氧键在高温下也会形成碳氧双键，形成一氧化碳气体。这样使得氧化石墨烯中的O被除去，从而得到石墨烯。 The surface of graphene oxide is mainly composed of -C-OH or carbon-carbon epoxy bond. Under high temperature conditions, two -OH will lose one water molecule, and at the same time form a carbon-oxygen double bond, and the carbon-oxygen double bond will be formed. Carbon monoxide gas, carbon-carbon epoxy bond also forms a carbon-oxygen double bond at a high temperature to form a carbon monoxide gas. This causes O in the graphene oxide to be removed, thereby obtaining graphene.
上述热处理过程，可以选择 H2 与 Ar 的混合气氛。In the above heat treatment process, a mixed atmosphere of H 2 and Ar can be selected.
步骤 S10 中的石墨烯和氧化石墨烯可以通过如下步骤制得： The graphene and graphene oxide in step S10 can be obtained by the following steps:
提供石墨： Provide graphite:
购买纯度超过 99.5% 的石墨。 Purchase graphite with a purity of over 99.5%.
使用石墨制备氧化石墨烯： Preparation of graphene oxide using graphite:
一般的，可以通过 Hummers 法制备氧化石墨，即将 S10 得到的石墨、高锰酸钾和高浓度强氧化性酸（硫酸或硝酸）置于同一容器中水浴或油浴加热，待充分氧化后取出，先用双氧水还原高锰酸钾，在用蒸馏水或盐酸洗涤产物数次，干燥后得到氧化石墨。 In general, graphite oxide can be prepared by the Hummers method, that is, S10 The obtained graphite, potassium permanganate and high-concentration strong oxidizing acid (sulfuric acid or nitric acid) are heated in a water bath or an oil bath in the same container, and are taken out after being fully oxidized, firstly reducing potassium permanganate with hydrogen peroxide, using distilled water or The product was washed several times with hydrochloric acid and dried to obtain graphite oxide.
通过对 Hummers 法进行一些改进制备氧化石墨烯，提高产率和产物纯度，改进后的制备过程包括如下步骤。 By Hummers The process is carried out to improve the preparation of graphene oxide to improve the yield and product purity. The improved preparation process comprises the following steps.
首先，将石墨、过硫酸钾和五氧化二磷按照质量比 2 ： 1 ： 1 加入到 60~85℃的浓硫酸中，搅拌均匀后自然冷却，洗涤至中性后干燥，得到预处理的混合物。 First, add graphite, potassium persulfate and phosphorus pentoxide to the mass ratio of 2:1:1. In concentrated sulfuric acid at 60-85 ° C, the mixture is uniformly stirred and then naturally cooled, washed to neutrality and then dried to obtain a pretreated mixture.
其次，将所述预处理的混合物和高锰酸钾加入到浓硫酸中，保持温度低于 20 ℃ ， 30~40℃油浴1.5~2 h ，加入去离子水， 15min 后加入双氧水反应，抽滤、收集固体。 Secondly, the pretreated mixture and potassium permanganate are added to concentrated sulfuric acid to keep the temperature below 20 °C. 30~40 °C oil bath 1.5~2 h, add deionized water, add hydrogen peroxide reaction after 15 min, suction filtration and collect solid.
最后，将上述固体用稀盐酸洗涤，干燥，得到氧化石墨烯。 Finally, the above solid was washed with dilute hydrochloric acid and dried to obtain graphene oxide.
油浴的目的是为了更好的控制反应温度，在其他的实施方式中，也可以采用水浴。 The purpose of the oil bath is to better control the reaction temperature, and in other embodiments, a water bath can also be used.
液相还原氧化石墨烯制得石墨烯： Liquid phase reduction of graphene oxide to produce graphene:
首先，将氧化石墨烯与去离子水混合并分散成悬浊液。一般可以采用超声波超声分散氧化石墨烯。 First, graphene oxide is mixed with deionized water and dispersed into a suspension. Ultrasonic ultrasonic dispersion of graphene oxide can generally be employed.
其次，向上述悬浊液中加入还原剂，加热到 90~100℃ 进行热还原， 24~48h 后得到石墨烯悬液。还原剂采用具有一定热稳定性的可溶性化合物，一般的可以列举：水合肼、硼氢化钠和对苯二铵，优选为水合肼。 Next, a reducing agent is added to the suspension, and heated to 90-100 ° C for thermal reduction, 24~48h A graphene suspension is obtained afterwards. The reducing agent is a soluble compound having a certain thermal stability, and generally, hydrazine hydrate, sodium borohydride and terephthalic acid, preferably hydrazine hydrate are mentioned.
最后，将石墨烯悬液过滤后收集滤渣，依次用水、甲醇洗涤后干燥，得到石墨烯。 Finally, the graphene suspension was filtered, and the residue was collected, washed with water, methanol, and dried to obtain graphene.
这种多孔石墨烯材料的制备方法通过氧化石墨烯或石墨烯与造孔剂混合、压制得到复合物，然后使复合物中的造孔剂释放出气体后，若为氧化石墨烯则500~2000℃热处理，最后得到多孔石墨烯材料，这种制备方法工艺简便，制备出的多孔石墨烯材料比表面积大，有利于宏观加工处理，所得到的多孔石墨烯材料可以用作超级电容器和锂离子电池电极材料。 The preparation method of the porous graphene material is obtained by mixing graphene or graphene with a pore former and pressing to obtain a composite, and then releasing the pore former in the composite to release a gas, if it is graphene oxide, 500~2000 The heat treatment is carried out at °C, and finally the porous graphene material is obtained. The preparation method has simple process, and the prepared porous graphene material has a large specific surface area, which is favorable for macroscopic processing, and the obtained porous graphene material can be used as a supercapacitor and a lithium ion battery. Electrode material.
下面是具体实施例部分。  The following is part of the specific embodiment.
实施例 1 Example 1
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯→掺杂氧化石墨烯的复合物→多孔石墨烯材料 Graphite → graphene oxide → composite of doped graphene oxide → porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：通过改进的 Hummers 法制备氧化石墨烯，参照（ Journal of the American Chemical Society 《美国化学会志》， 1958 ， 80 ， 1339 ）。 (2) Preparation of graphene oxide: Preparation of graphene oxide by modified Hummers method, reference (Journal of The American Chemical Society, 1958, 80, 1339).
其具体步骤为将 20g 50 目石墨粉、 10g 过硫酸钾和 10g 五氧化二磷加入 80 ℃ 的浓硫酸中，搅拌均匀，冷却 6h 以上，洗涤至中性，干燥。将干燥后的样品加入 0 ℃ 、 230mL 的浓硫酸中，再加入 60g 高锰酸钾，混合物的温度保持在 20 ℃ 以下，然后在 35 ℃ 的油浴中保持 2h 后，缓慢加入 920mL 去离子水。 15min 后，再加入 2.8L 去离子水 ( 其中含有 50mL 浓度为 30% 的双氧水 ) ，之后混合物颜色变为亮黄色，趁热抽滤，再用 5L 浓度为 10% 的盐酸进行洗涤、抽滤、在 60 ℃ 真空干燥 48h 即得到氧化石墨烯。 The specific step is to add 20g of 50 mesh graphite powder, 10g of potassium persulfate and 10g of phosphorus pentoxide to 80 °C. In concentrated sulfuric acid, stir evenly, cool for more than 6h, wash to neutral, and dry. The dried sample was added to 0 ° C, 230 mL of concentrated sulfuric acid, and then 60 g of potassium permanganate was added, and the temperature of the mixture was maintained at After 20 ° C, then in an oil bath at 35 ° C for 2 h, slowly add 920 mL of deionized water. After 15 minutes, add 2.8L of deionized water (containing 50mL) The concentration of the hydrogen peroxide is 30%, then the color of the mixture turns bright yellow, filtered while hot, washed with 5L of 10% hydrochloric acid, suction filtered, and dried under vacuum at 60 °C for 48h. That is, graphene oxide is obtained.
（ 3 ）将氧化石墨烯与干冰粉末在低于 -40 ℃ 的条件下混合，在一定的压力下混合，压制成块状材料。 (3) Graphene oxide and dry ice powder at less than -40 °C Mix under the conditions, mix under a certain pressure, and press into a block material.
（ 4 ）然后逐步升温到室温条件下，真空干燥，然后 500 ℃ 热处理，钝化得到多孔石墨烯材料。 (4) Then gradually heating to room temperature, vacuum drying, and then heat treatment at 500 °C to passivate the porous graphene material.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例1制得的多孔石墨烯材料比表面积as 为136.14m2 /g，平均孔径dp 为8.0156nm，孔比表面积ap 为264.88m2 /g。Measurement results: The porous graphene material obtained in Example 1 had a specific surface area a s of 136.14 m 2 /g, an average pore diameter d p of 8.0156 nm, and a pore specific surface area a p of 264.88 m 2 /g.
实施例 2 Example 2
本实施例通过石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing porous graphene material by graphene in this embodiment is as follows:
石墨 →氧化石墨烯 →石墨烯 →掺杂石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Graphene → Graphene-doped composite → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）制备石墨烯：氧化石墨烯 100mg 和去离子水 100mL 加入到 250mL 的圆底烧瓶中，此时溶液为棕黄色的悬浊液。然后将悬浊液用 150W 的超声波超声分散。最后向其中加入水合肼（ 1mL ， 98% ）并加热到 90 ℃ 反应 48h 。所得石墨烯过滤后依次用水 300mL 和甲醇 300mL 洗涤，在 80 ℃ 下真空干燥箱中干燥 48h 。 (3) Preparation of graphene: graphene oxide 100mg and deionized water 100mL added to 250mL In a round bottom flask, the solution was a brownish yellow suspension. The suspension was then ultrasonically dispersed with ultrasonic waves of 150 W. Finally, hydrazine hydrate (1 mL, 98%) was added thereto and heated to 90 °C. 48h. The obtained graphene was filtered, washed with 300 mL of water and 300 mL of methanol successively, and dried in a vacuum oven at 80 ° C for 48 hours.
（ 4 ）将石墨烯与干冰粉末在低于 -40 ℃ 的条件下混合，在一定的压力下混合，压制成形成微米级别的颗粒。 (4) Graphene and dry ice powder at less than -40 °C The mixture is mixed under a certain pressure and pressed to form micron-sized particles.
（ 5 ）然后逐步升温到室温条件下，真空干燥，然后 2000 ℃ 热处理，钝化得到多孔石墨烯材料。 (5) then gradually warm to room temperature, vacuum drying, then 2000 °C Heat treatment, passivation to obtain a porous graphene material.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例2制得的多孔石墨烯材料比表面积as 为193.12m2 /g，平均孔径dp 为6.4984nm，孔比表面积ap 为273.94m2 /g。Measurement results: The porous graphene material obtained in Example 2 had a specific surface area a s of 193.12 m 2 /g, an average pore diameter d p of 6.4984 nm, and a pore specific surface area a p of 273.94 m 2 /g.
实施例 3 Example 3
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →掺杂氧化石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Composite of doped graphene oxide → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）将氧化石墨烯与碳酸铵溶液混合，除去溶剂，固化、压制成块状材料。 (3) Mixing graphene oxide with an ammonium carbonate solution, removing the solvent, solidifying, and pressing into a bulk material.
（ 4 ）然后在真空条件下，升温至 500 ℃ 热处理，使得碳酸铵热分解，真空除去部分分解产物，钝化后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (4) then warm to 500 °C under vacuum The heat treatment causes the ammonium carbonate to thermally decompose, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例3制得的多孔石墨烯材料比表面积as 为424.41m2 /g，平均孔径dp 为9.2264nm，孔比表面积ap 为655.9m2 /g。Measurement results: The porous graphene material obtained in Example 3 had a specific surface area a s of 422.41 m 2 /g, an average pore diameter d p of 9.2264 nm, and a pore specific surface area a p of 655.9 m 2 /g.
实施例 4 Example 4
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →石墨烯 →掺杂石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Graphene → Graphene-doped composite → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）石墨烯：氧化石墨烯 100mg 和去离子水 100mL 加入到 250mL 的圆底烧瓶中，此时溶液为棕黄色的悬浊液。然后将悬浊液用 150W 的超声波超声分散。最后向其中加入水合肼（ 1mL ， 98% ）并加热到 100 ℃ 反应 24h 。所得石墨烯过滤后依次用水 300mL 和甲醇 300mL 洗涤，在 80 ℃ 下真空干燥箱中干燥 48h 。 (3) Graphene: Graphene oxide 100mg and deionized water 100mL added to 250mL In a round bottom flask, the solution was a brownish yellow suspension. The suspension was then ultrasonically dispersed with ultrasonic waves of 150 W. Finally, hydrazine hydrate (1 mL, 98%) was added thereto and heated to 100 °C. 24h. The obtained graphene was filtered, washed with 300 mL of water and 300 mL of methanol successively, and dried in a vacuum oven at 80 ° C for 48 hours.
（ 4 ）将石墨烯与聚苯乙烯小球粉末混合，降低温度，固化、压制形成微米级别的颗粒。 (4) Mixing graphene with polystyrene pellet powder, lowering the temperature, solidifying and pressing to form micron-sized particles.
（ 5 ）然后在真空条件下，升温至 2000 ℃ ，使得聚苯乙烯热分解，真空除去部分分解产物，钝化得到多孔的石墨烯材料，然后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (5) then warm to 2000 °C under vacuum The polystyrene is thermally decomposed, partially decomposed in a vacuum, and passivated to obtain a porous graphene material, which is then washed by a solvent and dried to obtain a porous graphene material.
如图 3 所示为实施例 4 通过石墨烯与聚苯乙烯小球制得的多孔石墨烯材料的 SEM 照片，由图可以看出，多孔石墨烯材料具有多孔结构。 Figure 3 shows the SEM of the porous graphene material prepared by graphene and polystyrene beads. As the photograph, it can be seen that the porous graphene material has a porous structure.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例4制得的多孔石墨烯材料比表面积as 为134.66m2 /g，平均孔径dp 为7.9471nm，孔比表面积ap 为242.69m2 /g。Measurement results: The porous graphene material obtained in Example 4 had a specific surface area a s of 134.66 m 2 /g, an average pore diameter d p of 7.9471 nm, and a pore specific surface area a p of 242.69 m 2 /g.
实施例 5 Example 5
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →掺杂氧化石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Composite of doped graphene oxide → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）将氧化石墨烯与聚丙烯纳米微粒粉末混合，降低温度，固化、压制成块状材料。 (3) mixing graphene oxide with polypropylene nanoparticle powder, lowering the temperature, solidifying and pressing into a bulk material.
（ 4 ）然后在真空条件下，升温至 1200 ℃ 热处理，使得聚丙烯热分解，真空除去部分分解产物，钝化后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (4) then heat to 1200 °C under vacuum The heat treatment causes the polypropylene to be thermally decomposed, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例5制得的多孔石墨烯材料比表面积as 为632.41m2 /g，平均孔径dp 为10.232nm，孔比表面积ap 为712.52m2 /g。Measurement results: The porous graphene material obtained in Example 5 had a specific surface area a s of 632.41 m 2 /g, an average pore diameter d p of 10.232 nm, and a pore specific surface area a p of 712.52 m 2 /g.
实施例 6 Example 6
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →石墨烯 →掺杂石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Graphene → Graphene-doped composite → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）石墨烯：氧化石墨烯 100mg 和去离子水 100mL 加入到 250mL 的圆底烧瓶中，此时溶液为棕黄色的悬浊液。然后将悬浊液用 150W 的超声波超声分散。最后向其中加入水合肼（ 1mL ， 98% ）并加热到 95 ℃ 反应 36h 。所得石墨烯过滤后依次用水 300mL 和甲醇 300mL 洗涤，在 80 ℃ 下真空干燥箱中干燥 48h 。 (3) Graphene: Graphene oxide 100mg and deionized water 100mL added to 250mL In a round bottom flask, the solution was a brownish yellow suspension. The suspension was then ultrasonically dispersed with ultrasonic waves of 150 W. Finally, hydrazine hydrate (1 mL, 98%) was added thereto and heated to 95 °C. 36h. The obtained graphene was filtered, washed with 300 mL of water and 300 mL of methanol successively, and dried in a vacuum oven at 80 ° C for 48 hours.
（ 4 ）将石墨烯与碱式碳酸铜粉末混合，降低温度，固化、压制形成微米级别的颗粒。 (4) Mixing graphene with basic copper carbonate powder, lowering the temperature, solidifying and pressing to form micron-sized particles.
（ 5 ）然后在真空条件下，升温至 1800 ℃ ，使得碱式碳酸铜热分解，真空除去部分分解产物，钝化得到多孔的石墨烯材料，然后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (5) then heat up to 1800 °C under vacuum The basic copper carbonate is thermally decomposed, partially decomposed in a vacuum, and passivated to obtain a porous graphene material, which is then washed by a solvent and dried to obtain a porous graphene material.
用自动吸附仪 ( 日本 BEL 公司生产的 Belsorp Ⅱ 型比表面积测试仪 ) 测定多孔石墨烯材料在 77K 下的 N2 吸附等温线，用 BET ， t-Plot 和 BJH 法分别计算多孔石墨烯材料的比表面积，孔容以及孔径分布。测量前对样品进行 150 ℃ 真空处理 10h ，测 P/P0=0.99 时的 N2 吸附量计算多孔石墨烯材料的总孔容。The N 2 adsorption isotherm of the porous graphene material at 77 K was measured by an automatic adsorption instrument (Belsorp II type specific surface area tester manufactured by BEL Corporation, Japan), and the ratio of the porous graphene material was calculated by the BET, t-Plot and BJH methods, respectively. Surface area, pore volume and pore size distribution. Before the measurement, the sample was subjected to vacuum treatment at 150 ° C for 10 h, and the total pore volume of the porous graphene material was calculated by measuring the N 2 adsorption amount at P/P0 = 0.99.
测量结果：实施例6制得的多孔石墨烯材料比表面积as 为901.25m2 /g，平均孔径dp 为12.547nm，孔比表面积ap 为845.12m2 /g。Measurement results: The porous graphene material obtained in Example 6 had a specific surface area a s of 901.25 m 2 /g, an average pore diameter d p of 12.547 nm, and a pore specific surface area a p of 845.12 m 2 /g.
实施例 7 Example 7
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →掺杂氧化石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Composite of doped graphene oxide → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）将氧化石墨烯与碳酸氢钠粉末混合，降低温度，固化、压制形成微米级别的颗粒。 (3) mixing graphene oxide with sodium hydrogencarbonate powder, lowering the temperature, solidifying and pressing to form micron-sized particles.
（ 4 ）然后在真空条件下，升温至 750 ℃ 热处理，使得碳酸氢钠热分解，真空除去部分分解产物，钝化后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (4) then warm to 750 °C under vacuum The heat treatment causes the sodium hydrogencarbonate to thermally decompose, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.
实施例 8 Example 8
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →石墨烯 →掺杂石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Graphene → Graphene-doped composite → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）石墨烯：氧化石墨烯 100mg 和去离子水 100mL 加入到 250mL 的圆底烧瓶中，此时溶液为棕黄色的悬浊液。然后将悬浊液用 150W 的超声波超声分散。最后向其中加入水合肼（ 1mL ， 98% ）并加热到 90 ℃ 反应 36h 。所得石墨烯过滤后依次用水 300mL 和甲醇 300mL 洗涤，在 80 ℃ 下真空干燥箱中干燥 48h 。 (3) Graphene: Graphene oxide 100mg and deionized water 100mL added to 250mL In a round bottom flask, the solution was a brownish yellow suspension. The suspension was then ultrasonically dispersed with ultrasonic waves of 150 W. Finally, hydrazine hydrate (1 mL, 98%) was added thereto and heated to 90 °C. 36h. The obtained graphene was filtered, washed with 300 mL of water and 300 mL of methanol successively, and dried in a vacuum oven at 80 ° C for 48 hours.
（ 4 ）将石墨烯与碳酸铵溶液混合，除去溶剂，固化、压制成块状材料。 (4) The graphene is mixed with the ammonium carbonate solution to remove the solvent, solidified, and pressed into a bulk material.
（ 5 ）然后在真空条件下，升温至 1750 ℃ ，使得碳酸铵热分解，真空除去部分分解产物，钝化得到多孔的石墨烯材料，然后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (5) then heat to 1750 °C under vacuum The ammonium carbonate is thermally decomposed, partially decomposed in a vacuum, and passivated to obtain a porous graphene material, which is then washed by a solvent and dried to obtain a porous graphene material.
实施例 9 Example 9
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →掺杂氧化石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Composite of doped graphene oxide → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）将氧化石墨烯与聚二甲基硅氧烷小球粉末混合，降低温度，固化、压制形成微米级别的颗粒。 (3) mixing graphene oxide with polydimethylsiloxane pellet powder, lowering the temperature, solidifying and pressing to form micron-sized particles.
（ 4 ）然后在真空条件下，升温至 1200 ℃ 热处理，使得聚二甲基硅氧烷热分解，真空除去部分分解产物，钝化后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (4) then heat to 1200 °C under vacuum The heat treatment causes the polydimethylsiloxane to thermally decompose, partially removes the decomposition product in a vacuum, is passivated, washed by a solvent, and dried to obtain a porous graphene material.
实施例 10 Example 10
本实施例通过氧化石墨烯制备多孔石墨烯材料的工艺流程如下： The process flow for preparing a porous graphene material by using graphene oxide in this embodiment is as follows:
石墨 →氧化石墨烯 →石墨烯 →掺杂石墨烯的复合物→多孔石墨烯材料 Graphite → Graphene oxide → Graphene → Graphene-doped composite → Porous graphene material
（ 1 ）石墨：纯度 99.5% 。 (1) Graphite: purity 99.5%.
（ 2 ）制备氧化石墨烯：同实施例 1 。 (2) Preparation of graphene oxide: same as in Example 1.
（ 3 ）石墨烯：氧化石墨烯 100mg 和去离子水 100mL 加入到 250mL 的圆底烧瓶中，此时溶液为棕黄色的悬浊液。然后将悬浊液用 150W 的超声波超声分散。最后向其中加入水合肼（ 1mL ， 98% ）并加热到 100 ℃ 反应 36h 。所得石墨烯过滤后依次用水 300mL 和甲醇 300mL 洗涤，在 80 ℃ 下真空干燥箱中干燥 48h 。 (3) Graphene: Graphene oxide 100mg and deionized water 100mL added to 250mL In a round bottom flask, the solution was a brownish yellow suspension. The suspension was then ultrasonically dispersed with ultrasonic waves of 150 W. Finally, hydrazine hydrate (1 mL, 98%) was added thereto and heated to 100 °C. 36h. The obtained graphene was filtered, washed with 300 mL of water and 300 mL of methanol successively, and dried in a vacuum oven at 80 ° C for 48 hours.
（ 4 ）将石墨烯与聚丙烯纳米微粒粉末混合，降低温度，固化、压制成块状材料。 (4) Mixing graphene with polypropylene nanoparticle powder, lowering the temperature, solidifying and pressing into a bulk material.
（ 5 ）然后在真空条件下，升温至 1600 ℃ ，使得聚丙烯热分解，真空除去部分分解产物，钝化得到多孔的石墨烯材料，然后通过溶剂洗涤，干燥得到多孔石墨烯材料。 (5) then warm to 1600 °C under vacuum The polypropylene is thermally decomposed, partially decomposed in a vacuum, and passivated to obtain a porous graphene material, which is then washed by a solvent and dried to obtain a porous graphene material.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (10)

  1. 一种多孔石墨烯材料，其特征在于，所述多孔石墨烯材料的孔径为1nm ~10μm，比表面积为100m2/g~2000m2/g。 A porous graphene material characterized in that the porous graphene material has a pore diameter of 1 nm to 10 μm and a specific surface area of 100 m 2 /g to 2000 m 2 /g.
  2. 如权利要求1所述多孔石墨烯材料，其特征在于，所述多孔石墨烯材料孔径50nm ~10μm占总体积20%~40%，2nm~50nm占总体积35%~55%, 1nm~2nm占总体积20%~25%。 The porous graphene material according to claim 1, wherein said porous graphene material has a pore diameter of 50 nm. ~10μm accounts for 20%~40% of the total volume, 2nm~50nm accounts for 35%~55% of the total volume, and 1nm~2nm accounts for 20%~25% of the total volume.
  3. 如权利要求1所述多孔石墨烯材料，其特征在于，所述多孔石墨烯材料的孔径为2~50nm，比表面积为150m2/g~1000m2/g。 1 The porous material as claimed in claim graphene, wherein the pore size of the porous material is graphene 2 ~ 50nm, specific surface area of 150m 2 / g ~ 1000m 2 / g.
  4. 如权利要求1所述多孔石墨烯材料，其特征在于，所述多孔石墨烯材料的孔比表面积为150 m2/g~2500m2/g。 The porous graphene material according to claim 1, wherein said porous graphene material has a pore specific surface area of from 150 m 2 /g to 2500 m 2 /g.
  5. 一种多孔石墨烯材料的制备方法，其特征在于，包括如下步骤：A method for preparing a porous graphene material, comprising the steps of:
    将石墨烯或氧化石墨烯与可以释放出气体的造孔剂混合、压制块状或粉末状颗粒的复合物；Mixing graphene or graphene oxide with a pore former capable of releasing a gas, and pressing a composite of bulk or powdery particles;
    加热所述复合物，使造孔剂释放出气体后，得到所述多孔石墨烯材料。The porous graphene material is obtained by heating the composite to release a gas from the pore former.
  6. 如权利要求5所述的多孔石墨烯材料的制备方法，其特征在于，所述造孔剂为干冰，加热温度使干冰气化。  The method for producing a porous graphene material according to claim 5, wherein the pore former is dry ice, and the heating temperature is used to vaporize dry ice.
  7. 如权利要求5所述的多孔石墨烯材料的制备方法，其特征在于，所述造孔剂为分解温度低于2000℃的有机高分子材料或有机小分子材料，使所述复合物中的造孔剂释放出气体的操作为：将所述复合物升温至500~2000℃，使得有机高分子材料或有机小分子材料热分解释放出气体。 The method for preparing a porous graphene material according to claim 5, wherein the pore former is an organic polymer material or an organic small molecule material having a decomposition temperature lower than 2000 ° C, so that the composite is made The operation of releasing the gas from the pore agent is to raise the temperature of the composite to 500 to 2000 ° C, so that the organic polymer material or the organic small molecule material is thermally decomposed to release the gas.
  8. 如权利要求 7 所述的多孔石墨烯材料的制备方法，其特征在于，所述的有机高分子材料为聚碳酸酯小球、聚苯乙烯小球、聚丙烯小球、聚乙炔小球、聚苯小球、聚二甲基硅氧烷小球、聚碳酸酯纳米微粒、聚苯乙烯纳米微粒、聚丙烯纳米微粒、聚乙炔纳米微粒、聚苯纳米微粒和聚二甲基硅氧烷纳米微粒中的一种或几种；Claim 7 The method for preparing a porous graphene material is characterized in that the organic polymer material is polycarbonate pellet, polystyrene pellet, polypropylene pellet, polyacetylene pellet, polyphenyl pellet, One of polydimethylsiloxane globules, polycarbonate nanoparticles, polystyrene nanoparticles, polypropylene nanoparticles, polyacetylene nanoparticles, polyphenyl nanoparticles, and polydimethylsiloxane nanoparticles Or several
    有机小分子材料为醋酸铵、碳酸铵、醋酸四甲基铵、硝酸铵、碳酸氢钠、碱式碳酸铜和高锰酸钾中的一种或几种。The organic small molecule material is one or more of ammonium acetate, ammonium carbonate, tetramethylammonium acetate, ammonium nitrate, sodium hydrogencarbonate, basic copper carbonate, and potassium permanganate.
  9. 如权利要求8所述的多孔石墨烯材料的制备方法，其特征在于，所述有机高分子材料的小球直径为10nm~1μm。 The method for producing a porous graphene material according to claim 8, wherein the organic polymer material has a small sphere diameter of 10 nm to 1 μm.
  10. 如权利要求1~4中任一项所述的多孔石墨烯材料，其特征在于，所述多孔石墨烯材料可以用作超级电容器或锂离子电池电极材料。 The porous graphene material according to any one of claims 1 to 4, wherein the porous graphene material can be used as a supercapacitor or a lithium ion battery electrode material.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102847510A (en) * 2012-08-31 2013-01-02 中国科学院金属研究所 Graphene-based water purification material, and preparation method and application thereof
JP5655161B2 (en) * 2011-12-09 2015-01-14 パナソニック株式会社 Nitrate reduction method, nitrate reduction catalyst, nitrate reduction electrode, fuel cell, and water treatment apparatus
US20150104372A1 (en) * 2013-10-11 2015-04-16 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Single-Step, Solvent-Free, Catalyst-Free Preparation of Holey Carbon Allotropes
JP2016503569A (en) * 2013-05-30 2016-02-04 エルジー・ケム・リミテッド Conductive material for secondary battery and electrode for lithium secondary battery including the same
EP2876082A4 (en) * 2012-07-23 2016-06-08 Univ Tsinghua Graduate School High-density high-rigidity graphene porous carbon material and preparation method and application thereof
US9960427B2 (en) 2013-05-30 2018-05-01 Lg Chem, Ltd. Conductive material for lithium secondary battery and electrode for lithium secondary battery including the same
CN108470648A (en) * 2018-06-20 2018-08-31 深圳清华大学研究院 Porous electrode piece and preparation method thereof and capacitor
US10367188B2 (en) 2015-01-09 2019-07-30 Semiconductor Energy Laboratory Co., Ltd. Storage battery electrode, manufacturing method thereof, storage battery, and electronic device

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9012522B2 (en) * 2011-06-15 2015-04-21 Massachusetts Institute Of Technology Foams of graphene, method of making and materials made thereof
ES2538604B1 (en) * 2013-11-22 2016-04-20 Universitat De València Preparation of corrugated and porous graphene from COF for use as supercapacitors
CN103601180B (en) * 2013-12-02 2016-08-17 深圳市贝特瑞新能源材料股份有限公司 A kind of Nano-size Porous Graphite alkene material and preparation method thereof
CN106232520B (en) * 2014-02-17 2020-12-11 威廉马歇莱思大学 Laser-induced graphene materials and their use in electronic devices
CN103787326B (en) * 2014-03-06 2015-06-17 南开大学 Preparation method of grapheme material with three-dimensional network structure
KR101604791B1 (en) * 2014-03-28 2016-03-21 경희대학교 산학협력단 Nano composite, method for preparing the same, and supercapacitor
KR101604792B1 (en) * 2014-03-28 2016-03-21 경희대학교 산학협력단 Nano composite, method for preparing the same, and supercapacitor
JP2015218085A (en) * 2014-05-16 2015-12-07 国立大学法人信州大学 Activated graphene monolith and production method of the same
CN106660806B (en) * 2014-07-24 2019-05-17 斯马特高科技有限公司 The method of graphene function hybrid material for synthetic silica coating
KR102189514B1 (en) * 2014-10-10 2020-12-11 도레이 카부시키가이샤 Graphene powder, electrode paste for lithium ion battery and electrode for lithium ion battery
KR101652965B1 (en) * 2014-10-24 2016-09-01 (주)티피에스 Manufacturing method of graphene oxide using ultrasonication and apparatus for the same
US10221069B2 (en) * 2014-11-03 2019-03-05 Research Institute Of Petroleum Industry Producing graphene and nanoporous graphene
CN104925785A (en) * 2015-03-13 2015-09-23 宁波南车新能源科技有限公司 Preparation methods of porous graphene and supercapacitor with porous graphene
WO2017029692A1 (en) * 2015-08-18 2017-02-23 Nec Corporation Porous Graphene Coated Oxygen-Containing Carbon Material for High Capacity and Fast Chargeable Anode of Lithium Ion Battery
US10230093B2 (en) 2015-09-25 2019-03-12 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing storage battery electrode
CN105329883A (en) * 2015-10-14 2016-02-17 南京邮电大学 Porous graphene preparation method
KR101801789B1 (en) * 2015-11-05 2017-11-28 한국과학기술연구원 Porous carbon materials and methods of manufacturing the same
CN105449210A (en) * 2015-11-18 2016-03-30 福建翔丰华新能源材料有限公司 Preparation method for porous graphene micro-sheet
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US9905373B2 (en) * 2016-01-04 2018-02-27 Nanotek Instruments, Inc. Supercapacitor having an integral 3D graphene-carbon hybrid foam-based electrode
US9966199B2 (en) * 2016-01-11 2018-05-08 Nanotek Instruments, Inc. Supercapacitor having highly conductive graphene foam electrode
CN105523547B (en) * 2016-01-25 2017-09-29 浙江大学 A kind of super flexible high heat conduction graphene film and preparation method thereof
CN105645399B (en) * 2016-03-15 2017-12-12 南京大学（苏州）高新技术研究院 A kind of preparation method of the high-performance super capacitor three-dimensional few layer porous graphene of classification self-similarity
KR20180016668A (en) * 2016-08-04 2018-02-19 동국대학교 산학협력단 p-PHENYLENEDIAMINE-REDUCED GRAPHENE OXIDE COMPOSITE, SUPERCAPACITOR INCLUDING THE SAME AND METHOD OF PREPARING THE SAME
US10890550B2 (en) * 2016-08-08 2021-01-12 B.G. Negev Technologies & Applications Ltd. At Ben-Gurion University High sensitivity broad-target porous graphene oxide capacitive vapor sensor
JP2019102711A (en) * 2017-12-05 2019-06-24 Ｔｐｒ株式会社 Capacitor
CN108003375A (en) * 2017-12-27 2018-05-08 桂林电器科学研究院有限公司 Preparation method of polyimide diaphragm of high air penetrability and products thereof
EP3530617A1 (en) * 2018-02-27 2019-08-28 Fundacio Privada Institut Catala de Nanociencia I Nanotecnologia (ICN2) Method of forming a porous graphene-based macroscopic structure
CN109103430B (en) * 2018-08-15 2021-07-02 宝鸡文理学院 Porous graphene coated and modified lithium ion battery positive electrode material and preparation method thereof
US11152620B2 (en) * 2018-10-18 2021-10-19 Global Graphene Group, Inc. Process for producing porous graphene particulate-protected anode active materials for lithium batteries
JP6782951B2 (en) * 2018-10-19 2020-11-11 Ｔｐｒ株式会社 Capacitors and electrodes for capacitors
WO2020080520A1 (en) * 2018-10-19 2020-04-23 Ｔｐｒ株式会社 Capacitor, and capacitor electrode
CN111435632B (en) * 2019-01-11 2021-11-09 中国石油大学(北京) Lithium ion capacitor and preparation method thereof
CN111659346A (en) * 2019-03-08 2020-09-15 天津大学 Haze collecting, absorbing and converting system based on primary battery principle
CN111391468B (en) * 2020-03-25 2021-10-22 海宁市和盛彩印有限公司 Composite technology of breathable film for outer package of drying agent
EP3978432A1 (en) 2020-10-02 2022-04-06 Institució Catalana De Recerca I Estudis Avançats (ICREA) Method to prepare graphene coated sponges, sponges obtained thereof, electrodes obtained from such sponges and uses of the sponges for water treatment
CN112174124A (en) * 2020-10-20 2021-01-05 大同通扬碳素有限公司 Porous graphene electrode and preparation method thereof
CN112545066B (en) * 2020-12-25 2024-03-29 海宁新纳陶科技有限公司 Graphene porous ceramic capable of heating, atomization core and preparation method thereof
JP2023002356A (en) 2021-06-22 2023-01-10 株式会社インキュベーション・アライアンス Graphene material and method for producing the same
CN113422005B (en) * 2021-06-23 2022-04-15 天目湖先进储能技术研究院有限公司 Porous electrode, preparation method thereof and lithium battery
EP4180027A1 (en) * 2021-10-26 2023-05-17 Tata Consultancy Services Limited Sunscreen composition containing visibly transparent biocompatible ultraviolet blocking polymer nanoparticles
CN114019172B (en) * 2021-11-15 2022-08-16 云南大学 Detection kit for disease protein marker based on peptide and antibody and application thereof
CN114497513A (en) * 2022-03-05 2022-05-13 青岛泰达华润新能源科技有限公司 Graphene negative electrode material for lithium ion battery and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050169829A1 (en) * 2004-02-03 2005-08-04 Sheng Dai Robust carbon monolith having hierarchical porosity
CN101454243A (en) * 2006-05-31 2009-06-10 促进科学E.V.麦克斯-普朗克公司 Porous carbon electrode with conductive polymer coating
CN102115069A (en) * 2010-12-20 2011-07-06 中国石油大学(北京) Graphene with porous structure and preparation method of graphene

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1226294B1 (en) * 1999-07-21 2011-06-29 Hyperion Catalysis International, Inc. Methods of oxidizing multiwalled carbon nanotubes
JP2003038953A (en) * 2001-07-31 2003-02-12 Toyota Central Res & Dev Lab Inc Hydrogen storage body and hydrogen storage apparatus
JP2005060849A (en) * 2003-08-11 2005-03-10 Toray Ind Inc Porous carbon fiber and method for producing the same
US8164881B2 (en) * 2006-05-31 2012-04-24 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Porous carbon electrode with conductive polymer coating
WO2009029984A1 (en) * 2007-09-03 2009-03-12 Newsouth Innovations Pty Limited Graphene
JP2010111547A (en) * 2008-11-07 2010-05-20 Sumitomo Chemical Co Ltd Method of manufacturing aluminum titanate-based porous fired body
US9053870B2 (en) * 2010-08-02 2015-06-09 Nanotek Instruments, Inc. Supercapacitor with a meso-porous nano graphene electrode

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050169829A1 (en) * 2004-02-03 2005-08-04 Sheng Dai Robust carbon monolith having hierarchical porosity
CN101454243A (en) * 2006-05-31 2009-06-10 促进科学E.V.麦克斯-普朗克公司 Porous carbon electrode with conductive polymer coating
CN102115069A (en) * 2010-12-20 2011-07-06 中国石油大学(北京) Graphene with porous structure and preparation method of graphene

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5655161B2 (en) * 2011-12-09 2015-01-14 パナソニック株式会社 Nitrate reduction method, nitrate reduction catalyst, nitrate reduction electrode, fuel cell, and water treatment apparatus
EP2876082A4 (en) * 2012-07-23 2016-06-08 Univ Tsinghua Graduate School High-density high-rigidity graphene porous carbon material and preparation method and application thereof
CN102847510A (en) * 2012-08-31 2013-01-02 中国科学院金属研究所 Graphene-based water purification material, and preparation method and application thereof
JP2016503569A (en) * 2013-05-30 2016-02-04 エルジー・ケム・リミテッド Conductive material for secondary battery and electrode for lithium secondary battery including the same
US9960427B2 (en) 2013-05-30 2018-05-01 Lg Chem, Ltd. Conductive material for lithium secondary battery and electrode for lithium secondary battery including the same
US20150104372A1 (en) * 2013-10-11 2015-04-16 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Single-Step, Solvent-Free, Catalyst-Free Preparation of Holey Carbon Allotropes
US10367188B2 (en) 2015-01-09 2019-07-30 Semiconductor Energy Laboratory Co., Ltd. Storage battery electrode, manufacturing method thereof, storage battery, and electronic device
US10923706B2 (en) 2015-01-09 2021-02-16 Semiconductor Energy Laboratory Co., Ltd. Storage battery electrode, manufacturing method thereof, storage battery, and electronic device
US11545655B2 (en) 2015-01-09 2023-01-03 Semiconductor Energy Laboratory Co., Ltd. Storage battery electrode, manufacturing method thereof, storage battery, and electronic device
US11881578B2 (en) 2015-01-09 2024-01-23 Semiconductor Energy Laboratory Co., Ltd. Storage battery electrode, manufacturing method thereof, storage battery, and electronic device
CN108470648A (en) * 2018-06-20 2018-08-31 深圳清华大学研究院 Porous electrode piece and preparation method thereof and capacitor
CN108470648B (en) * 2018-06-20 2020-07-28 深圳清华大学研究院 Porous electrode plate, preparation method thereof and capacitor

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